CN1323335A - 粘结dvd的热熔性粘合剂 - Google Patents
粘结dvd的热熔性粘合剂 Download PDFInfo
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Abstract
本发明涉及含有至少一种热塑性弹性体、至少一种烃树脂、至少一种聚α-烯烃和至少一种带有一个官能团的极性蜡的热熔性粘合剂。所说粘合剂适于数字化视频盘(DVD)的基片叠接的粘结,使制造DVD盘的费用十分低廉。这种粘结形式制造的DVD盘能满足所有的现代质量要求,在受热后和受潮老化后,DVD盘的储存介质仍具有很高的信息密度。
Description
本发明涉及粘结具有夹层结构的DVD盘的热熔性粘合剂和生产具有夹层结构的DVD盘的方法。
“DVD”是数字化多功能盘或数字化视频盘的缩写。它们是光学的储存介质,与已知的CD(光盘)相似。DVD与CD和其它更早的光学储存盘的主要区别是在DVD盘中有特别高的储存音乐、图像和数据信息的信息密度。这些储存介质较高的数据或信息密度对生产方法和为此所应用的材料提出了更高的要求。
图1示意表示了一个称之为“DVD”的可能结构。DVD主要是由相同的二片组成,在一片的表面上覆盖上一层信息膜,它的储存容量为4.7千兆字节。在图1中,带有信息的膜用“1”表示,不带有信息的盖膜用2表示,用于扫描信息所要求的激光束用7表示。
DVD盘的结构与现在通用的和一般熟悉的CD光盘的区别在于,DVD盘具有夹层结构形式。CD盘主要是由聚碳酸酯和聚甲基丙烯酸酯组成的1.2mm厚的圆盘,而DVD盘是由2片,每片均是0.6mm厚的目前仅用聚碳酸酯制成的片组成。通过一个改良的数据结构和用小波长的激光,使DVD盘的信息膜可以含有约4.7千兆字节的信息,而通常的CD盘只能储存约640兆字节的信息。
DVD盘的夹层结构是指2层膜1和2必须相互结合。根据较早的技术,应用在溶剂基础上的粘合剂将这二层膜相互粘结。目前建议应用热熔性粘合剂、UV-可固化的无溶剂的粘合乳剂和UV-可交联的热熔性粘合剂。
为了生产DVD盘,下述操作步骤是绝对必要的:
*必须用注塑法生产聚碳酸酯或聚甲基丙烯酸酯片坯件;
*在带有信息膜的片坯件1上涂覆一层反射膜。这层膜一般是通过真空中蒸镀的一层反射膜,例如铝膜;
*反射膜必须在涂覆后直接进行防腐蚀的保护,因此在一个已公开的实施例中,在这层反射膜上通过UV辐射固化覆盖一层漆膜。还有一种供选择的方法是覆盖一层由热塑性物质组成的保护层;
*在没有信息膜的片坯件2上,可根据不同的方法印上图像或文字信息;
*将一张坯件1和一张坯件2用粘合剂粘结。
DE-A-3224647公开了一种关于视频光盘或数字采音盘的生产方法。该专利建议,载有信息的膜在用铝涂上反射膜后,再覆盖一层热塑性成膜剂组成的保护膜,它在规定的温度下熔化,后在室温下固化。在一个实施例中,该热塑性成膜剂同时也是粘合二块片坯件的粘合剂。在另一个实施例中,该成膜剂用另一种粘合剂涂层,该粘合剂在室温下有粘性,藉助这种粘合剂使二片坯件互相粘合。但是DE-A-3224647没有给出任何有关热塑性成膜剂的组成或在室温下有粘性的粘合剂的组成。此外DE-A-3224647也没有任何说明该粘合剂是否适用于生产DVD。
DE-A-3246857公开了一种光盘,它包含一对基片,其中至少在一个基片的表面上具有信息压印。在信息压印膜上涂有一层金属反射膜,在这金属反射膜上再覆盖一层树脂保护膜。在树脂保护膜上面还有一层粘合剂层,它用于叠接粘合二张基片。DE-A-3246857建议应用热熔性粘合剂作为粘合剂,它含有一种或多种热塑性的弹性体组成的混合物作为基本聚合物。此外从DE-A-3246857得知,其中公开的热熔性粘合剂含有增粘剂树脂和添加剂,如填料、抗氧化剂或UV-吸收剂,这些添加剂用来提高粘合剂的耐热性和耐气候性。此外为了对蒸镀的金属膜没有负面作用,该文献还告知粘合剂的熔体粘度,在160℃时不要超过1000Pa.s,但是没有告知该粘合剂是否适用于制造DVD盘。
根据DE-A-3840391的教导,应用热熔性粘合剂制造视频盘或数字音频盘时,由于它们的热稳定性较差,因此应用是有问题的。该文献还告知,应用UV-可固化的单体组分作为粘合剂可导致基片被腐蚀。DE-A-3840391建议,在粘结基片生产视频盘时,应用UV-可交联的热熔性粘合剂,但是它没有指示,UV-可交联的热熔性粘合剂是否适用于生产DVD。
正如上面提及的,DVD盘与已知的CD或光盘(也可称之为激光光盘)相比,它的储存介质具有更高的信息密度或数据密度,因此DVD的生产对生产方法和应用的材料,如对粘合剂,提出更高的要求。在EP-A-0735530中详细说明了这方面的问题。由于DVD盘的信息密度高和盘直径小,所以在放入电唱机时,盘的光学平面校正的可容许的偏差要显著地小于通常的激光光盘,由此盘校正只要有一个很少的偏差,就会明显地影响再现的信息信号。由于这个原因,虽然DVD盘的二片单层膜是由约0.6mm厚的塑料压制品组成,但放入电唱机的DVD在相对长时间播放的热负荷下,在电唱机中必须保持不发生弯曲或偏斜。UV-固化的粘合剂,因为它在固化后大部分都很脆,所以在冲击负荷下常会粘附失效。而且大多数的UV-固化粘合剂和其它的反应粘合剂有一种相对高的自身收缩性,由于生成的粘合剂对反射层的作用力会对DVD的储存信息和工作可靠性造成损害。基于这个原因EP-A-0735530建议应用由一种热熔性粘合剂和一种乳液反应粘合剂的复合剂粘结二张基片制造DVD盘。但是没有提及所建议的热熔性粘合剂的组成。所建议的乳液反应粘合剂是阳离子型的聚合物UV-固化粘合剂。
WO-A-98/40883公开了一种在160℃具有熔体粘度为100,000mPa.s的热熔性粘合剂,它用来粘结夹层式的数字化视频盘(DVD)。在一些优选的实施例中,热熔性粘合剂含有一些用以达到改善图像显示或文字信息的能造成强烈反差的颜料。但WO-A-98/40883没有给出关于粘结后DVD的耐热性的说明,特别是考虑到对DVD所储存的信息应尽可能有不失真的扫描可能性。
JA-A-09208919公开了用于光盘的热熔性粘合剂的组成,它基本上由三种成分组成,其中第一种成分是苯乙烯-二烯烃嵌段共聚物或其氢化衍生物的苯乙烯树脂;第二种成分在松香树脂、萜烯树腊或石油树脂基础上的增粘剂,增粘剂的软化点至少为115℃,优选至少140℃。根据该文献的教导,热熔性粘合剂含有的另一种成分是蜡,优选石蜡、微蜡(Micro waxes)、低分子量的聚乙烯、低子分量的聚丙烯和非晶体的聚α-烯烃。特别建议应用在分子结构中没有官能团的蜡,因此建议优选使用具有最大的平均分子量为20000的晶体聚丙烯。JP-A-09208919还给出粘结剂性能标准的说明,如环球法软化点、熔体粘度、剥离强度、粘结强度和在较高温度下的蠕变,但是说明中没有允许应用这种粘合剂粘合DVD可用性的结论。
按照最新的对光学数据载体的质量控制要求,特别是对DVD的质量要求,在最近发展了一种测量系统,它可以通过三角测量法测定DVD的偏斜和变形。为此,测量反射的激光束的偏移,其中偏移度由一台接受点记录,它将偏移的光束的情况转化为电信号,然后再传送到一台模拟/数字转换器进行统计分析。这种类型的测量系统的一个例子是Conttec有限公司的光盘测量系统(Optical Disc Test System Advancedversion CODT-A)。
特别在热负荷和/或湿气影响下,所应用的粘合剂在相当大的程度上影响光盘的偏斜和变形。
从现有技术出发,本发明提供一种粘合剂,它不仅能经济地生产DVD,而且没有UV-固化粘合剂或至今已公开的热熔性粘合剂的缺点,能满足最新技术和DVD质量保证提出的严格要求。
本发明的目的是通过各项权利要求中的特征来实现的。本发明用于生产数字化视频盘(DVD)的热熔性粘合剂是主要基于以下成份:
a)至少一种热塑性弹性体;
b)至少一种烃树脂;
c)至少一种聚α-烯烃;
d)至少一种带有官能团的极性蜡。
根据本发明所应用的热熔性粘合剂除了上述主要的成分外,还含有增粘树脂、选择性的增塑剂、稳定剂/抗氧化剂、选择性的填充剂或填料、颜料、偶联剂或它们的混合物。
组分a)的热塑性弹性体的例子是热塑性聚氨酯(TPU),它一般以芳香二异氰酸酯为基础。特别适合的还有A-B-、A-B-A-、A-(B-A)n-B-和(A-B)n-Y-型的嵌段共聚物,其中A表示一种芳香聚乙烯嵌段,B嵌段包括一种橡胶类的中间嵌段,它可以部分或全部地氢化。这种嵌段共聚物的例子包括作为A的聚苯乙烯嵌段,作为B的主要是橡胶类的聚丁二烯和/或聚异戊二烯嵌段,Y可以是一种多官能团的化合物和n是一个至少为3的整数。为了改善热稳定性,中间嵌段B(如聚丁二烯嵌段或聚异戊二烯嵌段)可以选择性地部分氢化,由此原来存在的双键至少部分被排除。不同的生产厂提供作为SBS-(苯乙烯-丁二烯-苯乙烯)-共聚物或作为SIS-(苯乙烯-异戊二烯-苯乙烯)-共聚物、作为SEPS-(苯乙烯-乙烯-丙烯-苯乙烯)-共聚物、SEEPS-(苯乙烯-乙烯-乙烯-丙烯-苯乙烯)共聚物、或SEBS-(苯乙烯-乙烯-丁二烯-苯乙烯)共聚物的嵌段共聚物。
适合作为组分b)的烃树脂有脂族的、脂环族的或芳族的烃树脂或脂族-芳族烃树脂、石油烃树脂、以及它们的氢化产物和混合物。这些烃树脂是分子一般小于2000的已知聚合物。它们通过不饱和化合物C5馏份的聚合作用获得,在很多情况下在一个随后的步骤中氢化。具体的实例是以聚环戊二烯为基础、随后氢化的烃树脂,该类型的商品名称是Exxon公司的Escorez。类似的产品还有CdF Chemie公司生产的Norsolene、GOODYEAR公司生产的Wing-Tack、HERCULES公司生产的Hercures、Kristalex、Piccotac、REICHHOLD公司生产的Sta-tac或由Idemitsu公司生产的Sta-tac产品。
适宜作为组分c)的聚α-烯烃有带有分子量范围为5000和30000之间的乙烯、丙烯和/或1-丁烯的和无规立构的α-烯烃共聚物和三聚物。其中它们的分子量为数均分子量,可以按照DIN55672用凝胶渗透色谱法测定。这种类型的共聚物或三聚物也可以用上述的单体通过熟悉的连续齐格勒-低压聚合作用方法生产。它们也可称之为非晶形性的聚α-烯烃(APAO),虽然根据本发明特别优选使用的聚-α烯烃含有一部分有意义的晶体。部分结晶度可以藉助差热分析法(DTA)测定,因为部分结晶的聚α-烯烃在熔化曲线上有一个或多个最大峰值。
组分d)的带有官能团的极性蜡优选以乙烯和/或丙烯与丙烯酸、甲基丙烯酸和它们的C1至C4酯、衣原酸、富马酸、醋酸乙烯酯、一氧化碳、特别是马来酸和它们的混合物的聚合物为基础的分子量(GPc)的范围在约4000和80000之间的带有官能团的聚烯烃。其中优选的是带有皂化值或酸值在2和50mg KOH/g之间的用极性的单体接枝或共聚的乙烯、丙烯或乙烯-丙烯共聚合物。
根据本发明的热熔性粘合剂可选择性地含有已知的助剂和填加剂,其中有填充剂、颜料、增塑剂和稳定剂。作为填充剂可以应用如碳酸钙、碳酸钙镁、滑石、硅石、炭黑、锌白、氧化钛或其它的无机颜料。
可选择使用的增塑剂主要视所应用的聚合物成分而定,增塑剂有如加工油,特别是环烃加工油、石蜡油、蓖麻油、低分子量聚丁烯或聚异丁烯或聚异戊二烯和邻苯二甲酸的二烃基酯或烷基芳基酯。
用于减少氧化分解的稳定剂或抗氧化剂可应用大多数商品的抗氧化剂,如位阻酚和/或硫醚和类似物。为了达到更高的稳定性,将2种或多种不同化学组成的抗氧化剂组合在一起,是最有利的。
根据本发明的热熔性粘合剂含有:
*至少一种热塑性弹性体,其含量为10至40重量%,优选15至30重量%;
*至少一种烃树脂,其含量为15至50重量%,优选25至45重量%;
*至少一种聚α-烯烃,其含量为10至40重量%,优选15至30重量%;
*至少一种带有官能团的极性蜡,其含量为10至45重量%,优选15至35重量%;
*助剂和添加剂,其含量为0至10重量%,优选0.5至10重量%。
此处上述组分的总量应为100重量%。
下面藉助图2解释关于根据本发明的热熔性粘合剂的应用中主要的操作步骤:
1)用注塑法生产目前主要由聚碳酸酯组成的二片基片坯件;
2)基片坯件3在注塑过程中得到凹槽形式(pits)的信息膜,随后被涂覆一层反射膜,一般是由真空蒸镀如铝得到的金属膜;
3)第二张基片坯件2必要时也可以含有信息膜。在它的内表面上可以用不同的方法印刷图像显示或文字信息。例如在内表面上可以有多色镜面-影像版6。
4)在一片基片上或两片基片上涂以热熔性粘合剂5。然后将二片粘结成一张完整的DVD。
根据本发明的热熔性粘合剂在温度至少为140℃,优选160℃,一般用滚动涂覆方法涂到基片坯件上,层厚应大于或等于30μm。此处使用高溶体粘度,其范围在60000至130000mPa.s之间的粘合剂是十分有利的,因为即使在很高的加工速度下,这样的粘合剂也能非常干净地施用,而不会溢出DVD外部边缘区域。此外只有在高粘度情况下,才能避免形成抽丝。而且热熔性粘合剂具有很高的内聚力,用其制造的DVD在使用和操作时受到一种弯曲力作用后还能又快又好地恢复。
与现有技术的UV-可固化的粘合剂相比,应用根据本发明的粘合剂具有下述优点:
*热熔性粘合剂至少便宜4倍。而且热熔性粘合剂的粘结流程中的设备和仪器也比UV-可固化系统所必须的仪器和设备便宜;
*粘合剂可被染色或着色,由此DVD可有多种外观;
*热熔性粘合剂具有良好的粘附性能,特别是在冲击应力下和在很低的温度下仍保持有良好的粘附性能;
*热熔性粘合剂能较好地补偿聚碳酸酯基片的不准确性或形状偏差;
*正常情况下在生产应用热熔性粘合剂的过程中没有废品;
*不出现损害健康的气体,如臭氧或单体挥发物。
在更换产品或在停产时也没有消除热熔性粘合剂残余物的问题。这种残余物量是很小的,完全可以作为家庭废弃物处置。
下面结合一些优选的实施例对本发明作进一步的详细说明。在不超出本发明的范围的情况下,可以对本发明作出多种改动。组成单位中如没有特殊说明时,都是指重量%。
在一个可加热的混合和搅拌釜中,按下面表1中的组成在熔体中混合直至均匀。
软化点按照ASTM E28测定。粘度按ASTMD3236用型号为Brookfield RVT的粘度计,转轴27测定。耐热稳定性在2块重叠粘合的25×25mm聚碳酸酯组成的方块片上进行测定,在这粘合的两片上加上1360g的重量,随后以每10分钟升温5℃的加热速率加热。在多次试验中记录粘合失效的温度,此处“K”表示粘合失效。
在斑点试验中,在应用制造DVD的聚碳酸酯(PC)基片上涂以热熔性粘合剂点,随后进行剥离强度和冲击强度的手工测试。按照0(表示很坏)至15(表示很好)的级别评介。
从上述的结果中可以看到,根据本发明的热熔性粘合剂有很好的耐热稳定性和良好至很好的剥离强度和很好的耐冲击强度。
表1
实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
1)聚环戊二烯树脂 | 32.0 | 37.0 | 30.0 | 35.0 | 32.0 | 30.0 | 30.0 | 30.0 | ||
2)烃树脂 | 30.0 | 30.0 | ||||||||
2a)EPDM | 14.5 | |||||||||
3)苯乙烯-乙烯-丁烯-共聚物(SEBS) | 11.0 | 16.0 | 19.5 | 10.0 | 10.0 | 10.0 | ||||
4)苯乙烯-乙烯-丁烯-嵌段共聚物(SEBS) | 10.0 | |||||||||
5)苯乙烯-异戊二烯-嵌段共聚物,氢化 | 16.0 | 19.5 | 9.5 | 9.5 | 9.5 | 9.5 | ||||
6)APAO | 20.0 | 20.0 | 25.0 | 25.0 | 20.0 | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 |
7)Irganox 1010 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
8)丙烯-马来酸酐-共聚物 | 25.0 | |||||||||
9)乙烯-马来酸-共聚物 | 21.0 | 21.0 | 21.0 | |||||||
10)乙烯-马来酸酐-共聚物 | 25.0 | 25.0 | 25.0 | |||||||
11)乙烯-马来酸酐-共聚物 | 25.0 | 25.0 | 25.0 | |||||||
12)乙烯-丙烯酸乙酯-马来酸酐-三聚合物 | 10.5 | 10.5 | 10.5 | |||||||
100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | |
软化点℃ | 109.3 | 103.9 | 114.2 | 150.8 | 134.4 | 140.4 | 128.5 | 136.5 | 135.1 | 123.6 |
粘度160℃ | 51250 | 33350 | 39333 | 24120 | 840000 | 190750 | 56625 | 114000 | 66875 | 111000 |
粘度170℃ | ||||||||||
粘度180℃ | 23050 | 18500 | 17042 | 8700 | 140000 | 49333 | 23750 | 43750 | 33125 | 46250 |
粘度200℃ | 13475 | 9600 | 8000 | 4950 | 22250 | 17000 | 12594 | 23550 | 19094 | 16000 |
热稳定性(℃)PC/PC 0.02 N/mm2 | 82/80/84(K) | 81/80/76(K) | 86/86/85/81(K) | 76/78/86/81(K) | 80/80/85(K) | 90/91/91/84(K) | 81/80/86/86(K) | 87/87/86/86(K) | ||
PC(剥离/冲击) | 15/10 | 15/8 | 15/10 | 0/- | 15/15 | 15/15 | 15/15 | 12/- | 15/15 | 12/12 |
1)粘度:180℃,850mPas
2)以氢化二环戊二烯为基础,粘度:4900mPas/180℃
3)粘度:600mPas/25℃(在20%甲苯中)
4)粘度:200mPas/25℃(在20%甲苯中)
5)粘度:30mPas/30℃(在10%甲苯中)
6)熔体粘度:8000mPas/190℃,分子量(GPC)11600
7)抗氧化剂(Ciba Specialty Chemicals)
8)分子量(GPC)3900:酸值45mg KOH/g
9)分子量(GPC)5600:酸值2mg KOH/g
10)填料聚合物,粘度:600mPas/140℃,皂化值:4mg KOH/g
11)填料聚合物,粘度:4200mPas/140℃,皂化值:34mg KOH/g
12)热熔指数200g/10分,酸值17mg KOH/g,共聚单体量9%。
根据本发明的热熔性粘合剂和一种按现有技术制造的热熔性粘合剂(类似JP-A-09208919生产的产品)在老化前后用ODT-A-测量方法对偏斜和变形进行对比试验。在老化试验中,经粘合的DVD测试在80℃和相对湿度95%下放置96小时,在测试前调整到正常的大气条件下放置24小时。其中测试的DVD在一台Krauss-Maffei公司的注塑机中制造和在一台商购的Hotmelt-Bonder上涂热熔性粘合剂。ODT-A-测量是在一台Conttec公司的测试仪器上进行。测量结果见下述的表2。对于120mm的DVD-RAM,在径向方向(变形)的最大和最小的偏差值为0.70°,而切线方向(偏斜)最大和最小偏差为0.30°。如下表2可以看出,根据本发明的实施例极好地满足了在老化前后的要求。根据现有技术的热熔性粘合剂粘合的DVD在老化后其偏斜值和变形值很高。
表2
11 | 12 | 13 | 对照样品1 | 对照样品2 | |
径向弯曲(变形)老化前 | |||||
最小值(度) | -0.27 | -0.18 | -0.30 | 未提供 | 未提供 |
最大值(度) | 0.04 | 0.26 | 0.24 | 未提供 | 未提供 |
老化后 | |||||
最小值(度) | -0.62 | -0.53 | -0.64 | -0.27 | -1.74 |
最大值(度) | -0.11 | 0.16 | 0.08 | 1.47 | 0.68 |
切线弯曲(偏斜)老化前 | |||||
最小值(度) | -0.23 | -0.20 | -0.28 | 未提供 | 未提供 |
最大值(度) | 0.07 | 0.16 | 0.09 | 未提供 | 未提供 |
老化后 | |||||
最小值(度) | -0.27 | -0.24 | -0.29 | -0.48 | -0.48 |
最大值(度) | 0.10 | 0.09 | 0.13 | 0.81 | 0.11 |
Claims (8)
1.热熔性粘合剂在生产数字化视频盘(DVD)中的应用,所述热熔性粘合剂基于:
a)至少一种热塑性弹性体;
b)至少一种烃树脂;
c)至少一种聚α-烯烃;
d)至少一种带有官能团的极性蜡。
2.根据权利要求1的应用,其特征在于,从苯乙烯-二烯烃嵌段共聚物、苯乙烯-异戊二烯-苯乙烯、苯乙烯-丁二烯-苯乙烯和它们的至少部分氢化的衍生物或它们的混合物中选择一种或多种热塑性弹性体作为a)的组份。
3.根据权利要求1的应用,其特征在于,从脂环族的烃树脂、芳族的烃树脂、脂族的烃树脂、脂族/芳族的烃树脂、石油烃树脂、它们的氢化产品和上述树脂混合物中选择一种作为b)的组份。
4.根据权利要求1的应用,其特征在于,从乙烯、丙烯和/或丁烯的无规立构α-烯烃-共聚合物和三聚物中选择一种作为c)的组分,其分子量范围在5000和30000之间。
5.根据权利要求1的应用,其特征在于,从带有官能团的聚烯烃,其分子量范围从4000至80000中选择一种作为d)的组分,所述聚烯烃是以乙烯和/或丙烯与丙烯酸、甲基丙烯酸、它们的C1至C4-酯、马来酸、衣原酸、富马酸、乙酸乙烯酯、一氧化碳或它们的混合物的聚合物为基础的。
6.根据权利要求5的应用,其特征在于,组分d)的聚合物具有2至50mg KOH/g之间的皂化值或酸值。
7.根据上述权利要求中任一项所述的应用,其特征在于,热熔性粘合剂含有其它一般的助剂和添加剂,它们是填充剂、颜料、增塑剂、增粘树脂、抗老化剂,特别是抗氧化剂和/或UV-稳定剂、偶联剂或它们的混合物。
8.生产数字化视频盘(DVD)的方法,其特征是包括下述主要的步骤:
a)在基片坯件上覆盖信息膜;
b)在信息膜上涂覆一层光反射膜,然后选择性地覆盖一层防腐蚀膜;
c)在反射膜上涂覆根据权利要求1至7中任一项所述的热熔性粘合剂层;
d)选择性地在基片内层印上图像文字;
e)选择性地在印刷层上涂覆热熔性粘合剂层;
f)在挤压下藉助热熔性粘合剂层将二片基片粘合。
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DE19848146A DE19848146C2 (de) | 1998-10-20 | 1998-10-20 | Verwendung eines Schmelzklebstoffs zur Verklebung von DVDs und Verfahren zu deren Herstellung |
DE19848146.2 | 1998-10-20 |
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CN1323335A true CN1323335A (zh) | 2001-11-21 |
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CN99812140A Pending CN1323335A (zh) | 1998-10-20 | 1999-10-09 | 粘结dvd的热熔性粘合剂 |
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US (1) | US6767424B1 (zh) |
EP (1) | EP1135449B1 (zh) |
JP (1) | JP2002527600A (zh) |
KR (1) | KR100612640B1 (zh) |
CN (1) | CN1323335A (zh) |
BR (1) | BR9914669A (zh) |
CA (1) | CA2384280A1 (zh) |
DE (2) | DE19848146C2 (zh) |
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- 1999-10-09 KR KR1020017005007A patent/KR100612640B1/ko not_active IP Right Cessation
- 1999-10-09 BR BR9914669-0A patent/BR9914669A/pt not_active Application Discontinuation
- 1999-10-09 EP EP99950684A patent/EP1135449B1/de not_active Expired - Fee Related
- 1999-10-09 US US09/807,837 patent/US6767424B1/en not_active Expired - Fee Related
- 1999-10-09 JP JP2000577253A patent/JP2002527600A/ja active Pending
- 1999-10-09 WO PCT/EP1999/007579 patent/WO2000023537A1/de active IP Right Grant
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JP2002527600A (ja) | 2002-08-27 |
EP1135449B1 (de) | 2004-12-15 |
CA2384280A1 (en) | 2000-04-27 |
KR100612640B1 (ko) | 2006-08-14 |
DE19848146A1 (de) | 2000-05-04 |
DE19848146C2 (de) | 2002-10-02 |
BR9914669A (pt) | 2001-07-17 |
US6767424B1 (en) | 2004-07-27 |
WO2000023537A1 (de) | 2000-04-27 |
EP1135449A1 (de) | 2001-09-26 |
KR20010080283A (ko) | 2001-08-22 |
TWI230190B (en) | 2005-04-01 |
DE59911294D1 (de) | 2005-01-20 |
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